EP0052927A2 - Structure en feuille étirée du type poly-1,3,-phénylène téréphtalate - Google Patents
Structure en feuille étirée du type poly-1,3,-phénylène téréphtalate Download PDFInfo
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- EP0052927A2 EP0052927A2 EP81304689A EP81304689A EP0052927A2 EP 0052927 A2 EP0052927 A2 EP 0052927A2 EP 81304689 A EP81304689 A EP 81304689A EP 81304689 A EP81304689 A EP 81304689A EP 0052927 A2 EP0052927 A2 EP 0052927A2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- This invention relates to a stretched film structure of an aromatic polyester of the poly-1,3-phenylene terephthalate type, which has excellent heat resistance, fire retardancy (especially self-extinguishing property) and electrical properties and high physical strength properties such as tensile strength and elongation at break, moderate flexibility, and a high degree of surface smoothness.
- this invention relates to a monoaxially or biaxially stretched film structure, or a heat-set product thereof, of an unstretched film of an aromatic polyester of the poly-1,3-phenylene terephthalate type, said aromatic polyester having an intrinsic viscosity, determined in p-chlorophenol at 50°C, of 0.4 to 2.0 and being composed of (A) polybasic carboxylic acid component units consisting of terephthalic acid units (a l ) and units (a 2 ) of a polybasic carboxylic acid other than terephthalic acid, the proportion of the units (a 2 ) being up to 25 mole% (more than 0 but not exceeding 25 mole%) based on the units (a l ) and (a 2 ) combined, and (B) polyol component units consisting of resorcinol units (b l ) and units (b 2 ) of a polyol other than resorcinol, the proportion of the units (b 2 ) being up to 25
- film structure denotes a film, a sheet and like structures.
- polyesters used to produce these stretched films and sheets include polyethylene terephthalate, polyethylene-2,6-naphthalate, and terephthalic acid/isophthalic acid/bisphenol A copolyester.
- polyesters have improved mechanical properties when formed into stretched films and sheets suitable for practical applications, they have low heat resistance.
- polyethylene terephthalate and polyethylene-2,6-naphthalate are flammable, they cannot be used in applications which require heat resistance or fire retardancy.
- the present inventors worked on the improvement of the aforesaid poly-1,3-phenylene terephthalate film.
- This work has led to the discovery that a stretched poly-1,3-phenylene terephthalate film not at all described in the above patent document can be easily produced, and that the resulting stretched film has excellent heat resistance, fire retardancy (especially self-extinguishing property) and electrical properties, excellent physical strength properties such as tensile strength and elongation at break, moderate flexibility, and a high degree of surface smoothness.
- the aromatic polyester (superpolyester) used in the invention constituting the stretched film structure of the poly-l,3-phenylene terephthalate type is composed of
- the aromatic polyester described above should also have an intrinsic viscosity, determined in p-chlorophenol at 50°C, of 0.4 to 2.0.
- the proportion of the polybasic carboxylic acid component other than terephthalic acid is preferably up to 20 mole% (more than 0 but not exceeding 20 mole%), and the proportion of the polyol other than resorcinol is preferably up to 20 mole% (more than 0 but not exceeding 20 mole%).
- the intrinsic viscosity of the aromatic polymer is preferably 0.45 to 1.8.
- the intrinsic viscosity is less than 0.4, satisfactory physical strengths such as tensile strength at break cannot be obtained. If it exceeds 2.0, stretching unevenness tends to occur to cause surface unevenness, and a film structure having a good degree of surface smoothness and a uniform thickness cannot be formed.
- the stretched film structure of the invention is obtained by monoaxially or biaxially stretching a melt- shaped unstretched film structure of the above aromatic polyester, and if desired heat-setting the stretched film structure.
- the stretching is carried out to such an extent that the resulting monoaxially or biaxially stretched film structure has a crystallinity of 15 to 55%. If the crystallinity is less than 15%, satisfactory physical strengths are difficult to obtain. If it exceeds 50%, flexural property and flexibility of the product are not satisfactory.
- the monoaxially or biaxially stretched or further heat-set film structure of the invention has a density of about 1.34 to about 1.45 g/ml, preferably 1.35 to 1.43 g/ml.
- the polybasic carboxylic acid component units (A) of the aromatic polyester used in this invention may contain a small proportion of units (a 2 ) of the polybasic carboxylic acid other than terephthalic acid in addition to the terephthalic acid units (a l ).
- the polybasic carboxylic acids may be dibasic, tribasic or higher carboxylic acids.
- the units (a 2 ) may be a combination of dibasic carboxylic acid units (a 2 -1) other than terephthalic acid units and tribasic or higher carboxylic acid units (a 2 -2), or at least one type of units (a 2 -l) or (a 2- 2).
- the proportion of the units (a 2 -2) is preferably up to 5 mole % (more than 0 but not exceeding 5 mole%), for example 0.01 to 5 mole%, especially 0.1 to 3 mole%.
- the aromatic polyester utilized in the present invention may contain a small proportion of units (b 2 ) of a polyol other than resorcinol such as the resorcinol units ( b l ).
- the polyol may be a diol, triol or higher polyol.
- the other polyol units (b 2 ) may be a combination of units (b2 1) of a diol other than resorcinol and units (b b -2) of a tri- or higher polyol, or at least one type of the units (b 2 -1) or units (b 2 -2).
- the units (b 2 -2) are used, their amount is preferably up to 5 mole % (more than 0 but not exceeding 5 mole %), for example 0.01 to 5 mole%, especially 0.1 to 3 mole%, in the polyol component units [B].
- the aromatic polyester used in this invention contains a hydroxycarboxylic acid, a polyester oligomer of an hydroxycarboxylic acid, or a polyester block polymer of a hydroxycarboxylic acid as a constituent component
- an ester of such a constituent component and with the aforesaid polybasic carboxylic acid is included within the category of the polybasic carboxylic acid component units (A).
- An ester of the aforesaid constituent with the aforesaid polyol is included within the category of the polyol component units (B).
- dibasic carboxylic acids other than terephthalic acid forming the units (a - -l) include aromatic dicarboxylic acids such as methylterephthalic acid, phenylterephthalic acid, phthalic acid, isophthalic acid, 4-methylisophthalic acid, 5-methylisophthaiic acid, 4-phenylisophthalic acid, 5-phenylisophthalic acid, naphthalenedicarboxylic acids (e.g., naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid and naphthalene-2,5-dicarboxylic acid), 4,4'-dicarboxydiphenyl ether, bis(4-carboxyphenoxy)methane, bis(4-carboxyphenoxy)ethane, bis(3-car
- tribasic or higher carboxylic acids forming the units (a 2- 2) include tribasic or higher aromatic carboxylic acids such as trimellitic acid, hemimellitic acid, pyromellitic acid, naphthalenepolycarboxylic acids (e.g., naphthalene-2,3,6-tricarboxylic acid, naphthalene-2,3,7-tricarboxylic acid, naphthalene-2,4,6-tricarboxylic acid, naphthalene-2,4,6,7-tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid and naphthalene-1,3,5,7-tetracarboxylic acid), mono(2,3-dicarboxyphenyl) terephthalate, mono(2,4-dicarboxyphenyl) terephthalate, mono(2,5-dicarboxyphenyl) terephthalate, mono(2,6-dicarboxyphen
- aromatic polyesters in accordance with this invention which contain units (a 1 -2) of the above-exemplified tribasic or higher carboxylic acids have a branched chain structure or a partially crosslinked structure. Because of this characteristic, the use of such polyesters as the aromatic polyester in the invention offers the advantage that stretched film structures having further improved impact strength and tear strength can generally be obtained.
- diols other than resorcinol which form the units (b 2 -1) include aromatic diols other than resorcinol, such as 4-methylresorcinol, 5-methylresorcinol, 1,3-bis(hydroxyethoxy)benzene, catechol, 4-methylcatechol, 5-methylcatechol, 4-ethylcatechol, 5-ethylcatechol, 4-isopropylcatechol, 5-isopropylcatechol, 1,2-bis(hydroxy- ethoxy)benzene, hydroquinone, methylhydroquinone, ethylhydroquinone, isopropylhydroquinone, tert-butylhydroquinone, 1,4-bis(hydroxyethoxy)benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyethoxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane
- Those aromatic polyesters in accordance with this invention which contain the units (b2-1) of diols other than the resorcinol have increased moldability in the production of stretched film structure, and the heat stability of the resulting stretched film structures is not reduced.
- Those aromatic polyesters in accordance with this invention which contain aliphatic diol component units have increased moldability in the production of stretched film structures, and the resulting stretched film structures have increased elongation, impact strength and tear strength.
- trihydric or higher alcohols forming the units (b 2 -2) include trihydric or higher aromatic alcohols such as pyrogallol, phloroglucinol, 2,2',4,4'-tetrahydroxydiphenyl sulfide, 3-hydroxyphenyl 2,3-dihydroxybenzoate, 3-hydroxyphenyl 2,4-dihydroxybenzoate, 3-hydroxyphenyl 2,5-dihydroxybenzoate, 3-hydroxyphenyl 2,6-dihydroxybenzoate, 3-hydroxyphenyl 3,4-dihydroxybenzoate, 3-hydroxyphenyl 3,5-dihydroxybenzcate, 4-hydroxyphenyl 2,3-dihydroxybenzoate, 4-hydroxyphenyl 2,4-dihydroxybenzoate, 4-hydroxyphenyl 2,5-dihydroxybenzoate, 4-hydroxyphenyl 3,4-dihydroxybenzoate, 4-hydroxyphenyl 3,5-dihydroxybenzoate, 1-hydroxy-2,3-bis(3-hydroxyphenoxy- carbonyl)benzene, l-
- Those aromatic polyesters in accordance with this invention which contain the above-exemplified units (b 2 -2) have a branched chain structure or a partially crosslinked structure, and stretched film structures prepared from these polyesters have increased elongation, impact strength and tear strength.
- the aromatic polyesters utilized in the present invention can be produced by various known methods.
- Examples of the manufacturing methods include (1) a method which comprises polycondensing the above-exemplified polybasic carboxylic acid and/or its functional derivative and the above-exemplified polyol and/or its functional derivative; (2) a method which comprises preparing from two or more polyesters produced by the method (1) a graft polymer or a block polymer by ester-interchange reaction or other reactions, thereby adjusting the composition of the final polyester to that specified hereinabove; (3) a method which comprises polymerizing the above-exemplified polybasic carboxylic acid and/or its functional derivative and the above-exemplified polyol and/or its functional derivative in the presence of at least one polyester produced by method (1) or other methods, and at the same time preparing a graft polymer of a block polymer by ester-interchange reaction or other reactions, thereby adjusting the composition of the final polyester to that specified hereinabove; (4) a method which comprises first reacting the above-exemplified polybasic carboxylic acid and/or
- Specific procedures of producing the polyesters by polycondensation (method (1) above) of the above-exemplified polybasic carboxylic acid and/or its functional derivative and the above-exemplified polyol and/or its functional derivative include, for example, (a) polycondensation in the molten state, (b) polycondensation in solution, (c) interfacial polycondensation, and (d) polycondensation by the aforesaid melting, solution, or interfacial method, followed by polycondensation in the solid state.
- polyesters prepared by the various methods exemplified above may be used as prepared. Or they can be used in the form of polyesters having stabilized molecular terminals obtained by esterifying the carboxyl or phenolic hydroxyl groups present in the molecular terminals of the resulting polyesters with monofunctional compounds such as monohydric alcohols or monobasic carboxylic acids. Or the polyesters having stabilized molecular terminals can be obtained by producing the polyesters by the above methods in the presence of such monofunctional compounds for molecular weight control.
- the film structure of the poly-1,3-phenylene terephthalate type in accordance with this invention is biaxially stretched.
- the stretch ratio is, for example, from 0.2 to 10, preferably from 0.3 to 7, especially preferably from 0.5 to 5.
- the stretch ratio is, for example, from 0.2 to 8, preferably from 0.3 to 6, especially preferably from 0.5 to 5, in the longitudinal direction (machine direction), and, for example, from 0.2 to 8.0, preferably from 0.3 to 6.0, especially preferably from 0.5 to 5.0, in the transverse direction (in a direction traversing the machine direction).
- the monoaxially or biaxially stretched film structure of the invention may have varying thicknesses, for example from about 2 microns to about 500 microns.
- the stretched film structure of the invention may be obtained by stretching an unstretched film of the specified aromatic polyester alone, or of a composition comprising the aromatic polyester and suitable additives.
- suitable additives include nucleating agents, inorganic fillers, lubricants, slip agents, antiblocking agents, stabilizers, antistatic agents, anticlouding agents, pigments, and dyes. These additives may be incorporated into the aromatic polyester as produced, or may be added during the production of the aromatic polyesters.
- nucleating agents examples include fine powders of inorganic materials such as talc, silica, kaolin, clay, bentonite, sericite, carbon, glass and gypsum, the oxides, sulfates, carbonates, phosphates, aromatic and aliphatic carboxylates of metals of Group I or II of the periodic table such as lithium, sodium, potassium, calcium, barium, strontium and zinc, and polyalkylene glycols.
- the proportion of the nucleating agent used is, for example, 0.005 to 5% by weight, preferably 0.01 to 2% by weight, based on the polyester.
- inorganic fillers examples include calcium carbonate, silica, carbon black, kaolin, silicic acid, titanium dioxide, clay, bentonite, sericite, glass, gypsum, and talc.
- the proportion of the inorganic filler used is, for example, 0.005 to 5% by weight, preferably 0.01 to 2% by weight, based on the polyester.
- lubricants, slip agents and/or antiblocking agents examples include the aliphatic carboxylates (e.g., acetates), aromatic carboxylates (e.g., benzoates and terephthalates) of metals of Group I or II of the periodic table such as lithium, calcium, magnesium, barium and strontium, and inorganic materials such as silica, kaolin, calcium carbonate, silicic acid, clay, talc, and aluminum silicate.
- the proportion of these additives are, for example, from 0.005 to 5% by weight, preferably from 0.01-to 2% by weight, based on the polyester.
- the stabilizers may be those normally used for polyesters. Specific examples include phosphoric acid, phosphorous acid, hypophosphorous acid, phosphate esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, monobutyl phosphate and diethyl phosphate, phosphite esters such as trimethyl phosphite, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene and tetrakis(methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane.
- the proportion of the stabilizers used is, for example, 0.005 to 5% by weight.
- the pigments or dyes may be those normally used for polyesters. Their amounts may be those which can impart desired coloration.
- the stretched film structure of the poly-1,3-phenylene terephthalate resin in accordance with this invention is produced from an aromatic polyester having an intrinsic viscosity, determined in p-chlorophenol at 50°C, of 0.2 to 2.0 and composed of the polybasic carboxylic acid component units (A) and the polyol component units (B) described hereinabove.
- the stretched film structure of the invention can be produced by monoaxially or biaxially stretching an unstretched film structure of the above aromatic polyester and if desired, heat-setting the stretched film structure.
- Known conventional means for forming stretched films from film-forming synthetic resins can be utilized to produce unstretched film structures of the aromatic polyesters used in the invention, stretch the unstretched film structures and heat-set the stretched film structures.
- the aromatic polyester with or without the above-exemplified additives is molded by known melt molding means such as melt pressing or melt extrusion to form an unstretched film structure.
- the unstretched film structure is cooled to a temperature preferably below the glass transition point of the unstretched film structure, and then stretched monoaxially or biaxially at a temperature ranging from the glass transition point to the melting point of the film structure at the above-exemplified stretch ratio.
- the stretching temperature is, for example, about 140°C to about 290°C, preferably about 140°C to about 230°C.
- a solution of the aromatic polyester with or without the above-exemplified additives may be cast to form an unstretched film structure.
- a solvent as p-chlorophenol, o-chlorophenol or 2,4,6-trichlorophenol.
- the stretched film structure of the invention may be subjected to heat-setting treatment.
- Heat setting may be carried out by methods known per se. For example, it can be carried out under elongating conditions which cause elongating of the stretched film structure, under taut conditions which do not substantially elongate the stretched film structure nor.cause its relaxing, or under relaxing conditions which allow restricted or free shrinkage of the stretched film structure.
- the heat-setting is carried out under conditions which do not substantially cause elongation of the stretched film structure nor cause its relaxing.
- the heat-setting temperature can be suitably selected.
- it is the stretching temperature exemplified above or a temperature slightly higher than it.
- the heat-setting is carried out at a temperature of about 140 to about 300°C, preferably about 160 to about 280°C.
- the heat-setting time can also be suitably selected, and for example, it is about 5 seconds to about 600 seconds.
- the stretched film structure of the poly-1,3-phenylene terephthalate of the invention may be in the form of a monoaxially stretched or biaxially stretched film structure depending, for example, upon its end uses.
- a biaxially stretched blow-molded container obtained by blow molding in the biaxially oriented state also comes within the scope of the stretched film structure of the invention.
- the stretching can be performed by any known stretching operations, for example monoaxial stretching, biaxial stretching in which the unstretched film is stretched in the longitudinal direction and then in the transverse direction, biaxial stretching in which the unstretched film structure is stretched simultaneously in the longitudinal and transverse directions.
- the aforesaid biaxial stretching may be followed by further stretching in the longitudinal direction and/or the transverse directions either successively and/or simultaneously.
- the stretched film structure may be obtained by stretching the unstretched film structure by means of a stretching machine such as a tensile tester, a monoaxial stretcher or a biaxial stretcher at temperatures in the above-specified range.
- a monoaxially stretched film structure can be obtained by passing the unstretched film structure between at least one pair of heated rolls heated at the above temperature and having different speeds of rotation.
- the monoaxially stretched film structure can also be obtained by passing the unstretched film structure between two snap rolls having different speeds of rotation while bringing it into frictional contact with a hot plate kept at the above-specified temperature and placed between the snap rolls.
- an unstretched film structure or parison of the aromatic polyester with or without the above-exemplified additives is stretched in the longitudinal direction at the above temperature and then further stretched in the transverse direction, or simultaneously in the longitudinal and transverse directions at the above-specified temperature.
- the unstretched film structure is stretched biaxially by using a machine capable of performing stretching such as a tensile tester or a biaxial stretcher at the above-specified temperature; or passed through the aforesaid hot rolls to stretch it in the longitudinal direction and then passed through a similarly heated tenter to stretch it in the transverse direction; or passed between the above hot rolls to stretch it in the longitudinal direction and simultaneously passed through a tenter to stretch it in the transverse direction; or stretched biaxially by a tubular method at the above-specified temperature.
- the aforesaid biaxial stretching methods are repeatedly performed at the above temperature, or such methods are combined to perform stretching a number of times. It is also possible to perform biaxial stretching by blow molding a parison of the aromatic polyester at the above-specified temperature.
- the stretched film structure of the poly-1,3-phenylene terephthalate type in accordance with this invention has excellent heat resistance, fire retardancy (particularly self-extinguishing property) and electrical properties, high physical strength properties such as tensile strength and elongation at break, moderate flexibility, and a high degree of surface smoothness, and can be used in various applications which require these properties.
- the heat-set stretched film structure in accordance with this invention have the property of shrinking to different degrees at an elevated temperature depending upon the extent of heat-setting treatment, it can also be used as a shrinkable film.
- the stretched film structure of the invention is useful as electrical insulations, magnetic tapes, photographic films and metal vapor-deposited films. More specifically, it can be used for electrical insulation in electrical machines and instruments such as motors and transformers, electric cables and wires, condensers, insulative adhesive tapes and printed circuit boards.
- electrical tapes it can be used in electronic computers, videotape recorders, audio instruments.
- photographic films it can be used in radiography, electrophotography, motion picture films, and microfilms. It can also be used as substrates in printing, plate-making, copying, etc.
- metal- deposited films it can be used for gold and silver decorative yarns, labels, and condensers.
- the stretched film structure of the invention can also be used for packaging foodstuffs, etc.
- the sheet was further subjected to a flame resistance test.
- the molten surface of the sheet was carbonized, but its burning did not continue. Thus, this sheet was found to be self-extinguishing.
- Table 1 summarizes the properties of the stretched film structures obtained in Examples 1, 6, 16, 19, 24, 30, 31, 34, 36, 38, 42, 43, 44, 45 and 46 and Comparative Examples 1 to 4.
- Example 2 The same poly-1,3-phenylene terephthalate as prepared in Example 1, (1) was compression-molded under the same conditions as in Example 1, (2) to form a 1 mm- thick sheet. It was monoaxially stretched under the various stretching conditions as shown in Table 2 by an Instron tensile tester. The properties of the resulting monoaxially stretched sheets are also shown in Table 2.
- Example 1 The monoaxially stretched sheet obtained in Example 1 was heat-set by a high-temperature constant-humidity machine under the different heat-setting-conditions shown in Table 3. The properties of the heat-set products are also shown in Table 3. By the same flame resistance test as in Example 1, the heat-set product of the monoaxially stretched sheet in Example 6 was found to be self-extinguishing.
- Poly-1,3-phenylene terephthalate having an intrinsic viscosity of 0.77 was prepared by a method similar to that shown in Example 1, (1).
- the polyester was then compression-molded for 5 minutes at 310°C and 40 kg/cm 2 by means of a press former, and then quenched to form a transparent sheet having a thickness of 0.3 mm.
- the sheet was monoaxially stretched by an Intstron tensile tester under the streching conditions shown in Table 4. The properties of the monoaxially stretched films are also shown in Table 4.
- the monoaxially sketched film obtained in Example 11 was heat-set at 250°C for 60 seoonds using a high-temperature constants-humidity machine,
- the herat-set film had a tensile strength of 2-10 kg/cm 2 and an olonga- tion of 11% at break.
- the heat-set film was found to be selt- extinguishing.
- Poly-1,3-phenylene terephthalate having an intrinsic viscosity of 0.72 was prepared by a method similar to that shown in Example 1.
- the polyester was then compression-molded to form a sheet having a thickness of 1 mm.
- the sheet was then simultaneously stretched in the longitudinal and transverse directions by means of a biaxial stretching testing device. The stretching conditions and the properties of the resulting biaxially stretched sheets are shown in Table 5.
- Example 16 The biaxially stretched sheet of Example 16 was heat-set by means of a high-temperature constant-humidity machine.
- the heat-setting conditions and the properties of the heat-set products are shown in Table 6.
- Poly-1,3-phenylene terephthalate having an intrinsic viscosity of 0.72 was prepared by a method similar to that shown in Example 1, (1).
- the polyester was extruded from a T-die using a 40 mm extruder to form a sheet having a thickness of 0.5 mm.
- the unstretched sheet was then simultaneously stretched in the longitudinal and transverse directions by means of a biaxial stretching device. The stretching conditions and the properties of the resulting biaxially stretched films are shown in Table 7.
- the unstretched sheet having a thickness of 0.5 mm obtained in Example 21 was stretched first in the longitudinal direction and then in the transverse direction by means of a biaxial stretching device to form a biaxially stretched film.
- the stretching conditions and the properties of the biaxially stretched films a shown in Table 8.
- Example 31 The same melt polymerization as in Example 31, (1) was carried out except that the amounts of diphenyl terephthalate and diphenyl isophthalate charged were changed as shown in Table 9.
- the polyesters shown in Table 9 were obtained.
- Monoaxially stretched sheets were prepared form these polyesters in accordance with the method of Example 31, (2), and subjected to a tensile test. The results are shown in Table 9.
- the stretched film was heat-set at 250°C for 60 seconds by means of a high-temperature constant-humidity machine.
- the heat-set film had a tensile strength of 1850 kg/cm 2 and an elongation of 21% at break. After the heat-set film was maintained at 150°C for 24 hours, it had a tensile strength of 1860 kg/cm 2 .
- Example 1 The poly-l,3-phenylene terephthalate obtained in Example 1 was press-formed in the same way as in Example 1 to form a sheet having a thickness of 0.5 mm.
- the sheet had the properties shown in Table 1.
- Example 38 The polyester obtained in Example 38 composed of terephthalic acid, isophthalic acid, resorcinol and bisphenol A units was press-formed in the same way as in Example 1 to form a sheet having a thickness of 0.5 mm.
- the properties of the sheet are shown in Table 1.
- Poly-1,3-phenylene terephthalate having an intrinsic viscosity of 0.38 prepared by the same method as in Example 1 was press-formed in the same way as in Example 1, and then stretched monoaxially to 2.0 times at 180°C at a rate of 17X/min. to form a monoaxially stretched film.
- the properties of the film are shown in Table 1.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP140490/80 | 1980-10-09 | ||
JP14049080A JPS5764523A (en) | 1980-10-09 | 1980-10-09 | Polyester elongated filmy material or sheet-like material |
JP162618/80 | 1980-11-20 | ||
JP16261880A JPS5787328A (en) | 1980-11-20 | 1980-11-20 | Stretched film or sheet like object of polyester |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0052927A2 true EP0052927A2 (fr) | 1982-06-02 |
EP0052927A3 EP0052927A3 (en) | 1982-09-01 |
EP0052927B1 EP0052927B1 (fr) | 1987-01-07 |
Family
ID=26472979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81304689A Expired EP0052927B1 (fr) | 1980-10-09 | 1981-10-08 | Structure en feuille étirée du type poly-1,3,-phénylène téréphtalate |
Country Status (3)
Country | Link |
---|---|
US (1) | US4390683A (fr) |
EP (1) | EP0052927B1 (fr) |
DE (1) | DE3175805D1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2132626A (en) * | 1982-12-27 | 1984-07-11 | Sumitomo Chemical Co | Method for producing aromatic polyesters |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH062397B2 (ja) * | 1983-11-28 | 1994-01-12 | 三井石油化学工業株式会社 | 共縮合ポリエステル層を有する積層体 |
US4606930A (en) * | 1984-03-02 | 1986-08-19 | Sumitomo Chemical Company, Limited | Method for treating fibers |
US4584402A (en) * | 1984-10-29 | 1986-04-22 | Board Of Regents, The University Of Texas System | Dihydroxyacryl |
JPH0673179B2 (ja) * | 1985-06-14 | 1994-09-14 | ポリプラスチックス株式会社 | 磁気デイスク |
US4963402A (en) * | 1987-08-21 | 1990-10-16 | Minnesota Mining And Manufacturing Company | Films containing liquid crystalline polymers |
US5124184A (en) * | 1987-08-21 | 1992-06-23 | Minnesota Mining And Manufacturing Co. | Films containing liquid crystalline polymers |
US5039780A (en) * | 1988-11-08 | 1991-08-13 | Mitsui Petrochemical Industries, Ltd. | Copolyester having gas-barrier property |
ATE147321T1 (de) * | 1989-08-31 | 1997-01-15 | Mitsui Petrochemical Ind | Verfahren zur herstellung von blasgeformten gegenständen |
US5128091A (en) * | 1991-02-25 | 1992-07-07 | Xerox Corporation | Processes for forming polymeric seamless belts and imaging members |
IT1269849B (it) * | 1994-05-27 | 1997-04-15 | Enichem Spa | Procedimento per la preparazione di bottiglie riutilizzabili a partire da pet modificati |
US5545364A (en) * | 1994-10-06 | 1996-08-13 | Skc, Limited | Process for the preparation of heat resistant polyester film |
EP0897794B1 (fr) * | 1996-09-18 | 2003-09-03 | Teijin Limited | Film polyester pour doublure de metal et utilisation correspondante |
ID21527A (id) * | 1997-12-18 | 1999-06-24 | Toray Industries | Suatu film poliester dan metode pembuatannya |
US6518004B2 (en) * | 1999-12-27 | 2003-02-11 | Fuji Photo Film Co., Ltd. | Polyester support and silver halide photographic material |
DE10002165A1 (de) * | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Transparente, flammhemmend ausgerüstete, thermoformbare orientierte Folie aus kristallisierbaren Thermoplasten, Verfahren zu ihrer Herstellung und ihre Verwendung |
EP1186633B1 (fr) * | 2000-09-05 | 2005-06-08 | Toyo Boseki Kabushiki Kaisha | Feuille de polyester, sa préparation et laminé métallique préparé à partir de cette feuille, et boíte métallique et couvercle métallique produits à partir dudit laminé |
KR20020030007A (ko) * | 2000-09-29 | 2002-04-22 | 힐커트 | 결정성 열가소성 수지로부터 제조된 내가수분해성 투명이축배향 필름 및 그 제조방법 |
US7524447B2 (en) * | 2004-07-20 | 2009-04-28 | Sabic Innovative Plastics Ip B.V. | Method for manufacturing formable thermoplastic laminates |
US20100280152A1 (en) * | 2009-04-29 | 2010-11-04 | Spartech Corporation | Thermoformable and RF Sealable Plastic Packaging Material |
FR2978771B1 (fr) * | 2011-08-04 | 2013-09-27 | Michelin Soc Tech | Composition adhesive aqueuse a base de polyaldehyde et 2,2', 4,4'-tetrahydroxydiphenyl sulfide |
FR2978769B1 (fr) | 2011-08-04 | 2013-09-27 | Michelin Soc Tech | Composition adhesive aqueuse a base de polyaldehyde et de polyphenol |
FR2978770B1 (fr) | 2011-08-04 | 2013-09-27 | Michelin Soc Tech | Composition adhesive aqueuse a base de polyaldehyde et phloroglucinol |
KR101771729B1 (ko) * | 2012-07-25 | 2017-08-25 | 삼성전기주식회사 | 적층형 인덕터 및 적층형 인덕터의 보호층 조성물 |
WO2016116468A1 (fr) | 2015-01-21 | 2016-07-28 | Compagnie Generale Des Etablissements Michelin | Composition de caoutchouc à haute rigidité |
FR3031746A1 (fr) | 2015-01-21 | 2016-07-22 | Michelin & Cie | Composition de caoutchouc a haute rigidite |
FR3031745A1 (fr) | 2015-01-21 | 2016-07-22 | Michelin & Cie | Composition de caoutchouc a haute rigidite |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1291263A (fr) * | 1961-06-01 | 1962-04-20 | Thomson Houston Comp Francaise | Compositions de super-polyesters et leur mode de fabrication |
US3160602A (en) * | 1960-06-01 | 1964-12-08 | Gen Electric | Process of producing aromatic polyesters |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3875119A (en) * | 1970-12-22 | 1975-04-01 | Hiroshi Aoki | Product and process of producing biaxially oriented insulating film of polyethylene-2,6-naphthalate |
US3816368A (en) * | 1971-08-20 | 1974-06-11 | Asahi Chemical Ind | Film of a polyethylene-1,2-diphenoxy-ethane-4,4'-dicarboxylate copolymer |
US3778410A (en) * | 1972-09-28 | 1973-12-11 | Eastman Kodak Co | Process for preparing a final copolyester by reacting a starting polyester with an acyloxy aromatic carboxylic acid |
DE2460395A1 (de) * | 1974-12-20 | 1976-06-24 | Hoechst Ag | Gestreckte schlauchfolie aus polyaethylenterephthalat |
US4201856A (en) * | 1978-05-08 | 1980-05-06 | Eastman Kodak Company | Liquid crystal copolyesters containing terephthalic acid, 2,6-naphthalenedicarboxylic acid, hydroquinone and resorcinol |
-
1981
- 1981-10-06 US US06/309,101 patent/US4390683A/en not_active Expired - Lifetime
- 1981-10-08 DE DE8181304689T patent/DE3175805D1/de not_active Expired
- 1981-10-08 EP EP81304689A patent/EP0052927B1/fr not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3160602A (en) * | 1960-06-01 | 1964-12-08 | Gen Electric | Process of producing aromatic polyesters |
FR1291263A (fr) * | 1961-06-01 | 1962-04-20 | Thomson Houston Comp Francaise | Compositions de super-polyesters et leur mode de fabrication |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2132626A (en) * | 1982-12-27 | 1984-07-11 | Sumitomo Chemical Co | Method for producing aromatic polyesters |
US4542203A (en) * | 1982-12-27 | 1985-09-17 | Sumitomo Chemical Company, Limited | Method for producing branched aromatic polyesters |
Also Published As
Publication number | Publication date |
---|---|
DE3175805D1 (en) | 1987-02-12 |
EP0052927B1 (fr) | 1987-01-07 |
US4390683A (en) | 1983-06-28 |
EP0052927A3 (en) | 1982-09-01 |
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